DE1545447A1 - Continuous process for producing a methane-rich gas - Google Patents

Description

Dipi.-ing. Walter Meissner Dipi.-ing. Herbert Tischer

1 BERLIN 33, HERBERTSTRASSE 22 Λ C / r / ι η ' MUNICH

Telephone: 8 87 72 37 -Wire word: Invention Berlin f 0 4 0 4 4 / Postal checking account: W. M e Issner / Berlin West 12282

Bank account: W. Meissner, Berliner Bank A.-fr _f a8,.-.- ""'' Sm

Berlln-Halensee, KurfUretendamm 130 "". "' BERLIN d3 (Gl

Berlln-Halenaee, KurfUretendamm 130 ^ ₁ ._ ^ r- ^

^ J J> ; -i% ^ -.- H * rbertetraBe 22

UNEWALD), the

ir I 3

ase 232

INSTITUTE Of GAS TEOHIiOLOGY, 3424 Seuth State Street, HT Center Chicago, 111., 60610, USA

Continuous process for producing a methane rich

Gas

The invention relates to a "method for converting hydrocarbons by means of catalytic steam reforming in a gas high methane content ₀ The invention relates to insbesonä converting particular of hydrocarbons in a pipeline gas, that can be partially replaced completely by natural gas or the like. It is expedient that one is able to quickly and economically produce a gas with a high methane content, which can then be used for the purpose of satisfying maximum load peaks when the performance of pipelines carrying natural gas is inadequate.

A process for producing a substitute gas for natural gas stone is the cyclic, regenerative thermocracking of liquid petroleum products »In this process, however, the starting product is not completely converted into product gas and the gaseous portion is given a wide range of compounds that are used for relief purposes with maximum counterclaims In addition, the cyclic process has the disadvantage that it is not continuous. In order to produce gases with a high methane content, it has been proposed to reform light paraffin hydrocarbons by means of steam reforming, e.g. petroleum distillates, by adding them in the form of preheated hydrocarbon vapors with steam at pressures of up to 25 kg / om ^e and temperatures of 350-500 * 0

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in the presence of a nickel catalyst with the formation of a gas be brought to the reaction, the more than 50 moles of methane after Removing the Carbon Dioxide and Water Contains · In such operations it is necessary to apply a feed that is practically sulfur-free (less than 2 ppm) in order to operate the reaction vessel for a practical period of time

Higher sulfur contents in the paraffinic hydrocarbon lead to poisoning of the nickel catalyst in a relatively short time. These work even with feeds with a low sulfur content Process with relatively slow feed rates for the hydrocarbons, which results in large and costly reaction s result in · None of these procedures allow the use of olefinic or aromatic hydrocarbon feeds

The continuous process of the present invention for producing a methane-rich grass from hydrocarbon feeds is characterized in that the feed is vaporized, then the vaporized feed is evaporated with water vapor in the presence of a novel nickel-ion-earth-aluminum catalyst at elevated pressure and temperature from 343 to 566 ⁰ C is caused to react to form a gas which essentially contains methane, carbon dioxide, hydrogen and small amounts of carbon monoxide.

According to the invention it is possible to continuously and selectively To produce gas with a high methane content without causing inappropriate gas » ■ Shaped and liquid products are formed · This gas high Methane can be continuously and selectively produced so that the hydrocarbon feed is entirely in product gas is converted and at relatively low temperatures is worked, in which the methane yield is ice maximum and the efficiency of the entire process is high g »- 3 -

9098Ö6 / 1 239- ORIGINAL INSPECTED

Furthermore, according to the invention, the high methane grass becomes continuous and selectively from liquid hydrocarbon eschiokuK genes, the aromatic, olefinic and cyoloolefinic Components, with steam reforming of the light hydrocarbons and petroleum distillates is carried out using a novel catalyst The grass with a high methane content obtained according to the invention is mediated a process won »in which a low water vapor / hydrocarbon weight ratio is applied, but it is high enough to prevent carbon deposition Prevent the catalyst au, whereby the methane yield is maximum and the yield of carbon monoxide and hydrogen is kept to a minimum. The procedure is carried out at higher bridges and A gas with a maximum methane content obtained · Furthermore, the Feed rates for hydrocarbons only high, reducing the volume of the reaction vessel and equipment costs, but not at the expense the conversion of the charge into methane · According to the invention, the procedure is such that with water vapor gaseous hydrocarbons or liquid hydrocarbons or mixtures thereof are brought to implementation, the dea Reaction vessel in vapor form under the operating conditions of the reaction vessel in the presence of a Niekel alumina-aluminum catalyst can be delivered at elevated pressures, preferably at 5 to 30 kg / cm and temperatures of 343 up to 565 ° C · Typical hydrocarbon additions suitable according to the invention are liquefied petroleum gas, petroleum naphtha, natural gasoline, kerosene and similar petroleum distillates, with regard to these In the feed, the product gas does not contain more than 70 Μο1 · # methane after the carbon dioxide and water have been removed. That Feed water vapor to hydrocarbon weight ratio

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BATH ORIGINAL

I DH Dm * I - 4 -

is a maximum of about 4 * 5 si

The product gas obtained by means of this process can be used for grooving a demand gap or removing C0 _t . However, it is also contemplated to use the gas generally and continuously, in which case some or all of the CO _{8 will be} removed. When producing gas for general continuous use, it is preferred to use lower sulfur hydrocarbons .

The degree to which carbon dioxide is removed from the product gas is determined by the degree of interchangeability of the gas that is sought. In the following working examples, gas is cleaned to such an extent that the final CO ₈ content is 2 Mol.Jfc. However, this does not exclude the production of a gas whose final GO ₁ content is higher or lower than 2 mol%, and the production of such gases is also considered according to the invention. If one wants to mix the product gas according to the invention directly with pipeline gas (natural gas), this can be achieved without removing 00 _t depending on the requirements in question.

The following examples serve only to explain the subject matter of the invention and in no way limit the possible GO ₁ content that the finished gas has. When hydrocarbons are catalytically reformed with water vapor by means of the process of the invention, the following reactions practically reach the equilibrium states

CO + 3 H ₁ ± CH ₄ + H ₁ O (1)

CO + H ₈ O £ CO ₁ + H ₁ '(2)

The exact composition of the product gas is determined by the reaction conditions and the composition of the feed mixture of hydrocarbon and water vapor is determined, - 5 -

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In order to achieve a maximum yield of methane in the process according to the invention, the following working principles are applied: The process should be carried out at low temperatures and high pressures and the lowest possible weight ratios water vapor-hydrocarbon the Bgrohiekung be carried out. As the bridge increases, the methane yields and the yields increase of hydrogen. The yields decrease with increasing temperature of methane and the yields of hydrogen to “The yields of carbon dioxide vary only slightly depending on Temperature and pressure. The release of carbon monoxide increases with decreasing pressure and increases with temperature The molecular weight and composition of the feed will dictate the optimal temperature and pressure conditions as well the weight ratios of the steam-hydrocarbon feed ο It has been found that low molecular weight paraffin feeds to a product gas of higher methane content for any given. Set of reaction conditions. In selecting the weight ratio of the steam hydrocarbon feed, the following facts became apparent found. When increasing the molecular weight and the carbon content ' more steam is required to feed. at

more

An increase in the reaction temperature becomes necessary for w «e * g« a · water vapor. When the reaction pressure is reduced, there is less water vapor required The smallest weight ratio of water vapor to hydrocarbon, how it is required to prevent carbon deposition depends on the molecular weight and composition of the feed for any given set of work conditions of the reaction «vessels». It was found that it is possible at Waaaerdampf-hydrocarbon weight ratios of only 1.26 * 1 with a low Moellcular loading weight and high Hohlenwaseeretoffes like propane to work, whereby a gas with a high methane content is formed and calibrated

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no carbon is deposited on the catalyst. To achieve a close approximation to the equilibrium state iriBerhalb the temperature range from 343 to 566 ⁰ C, a very "active catalyst is needed · It has been found that the invention it is essential to a" new Nick el-tone, he de-aluminum catalyst to be used containing 25 to 60 wt # $ nickel, 10 to 60 wt # alumina and the remainder aluminum.

As a typical Seispiel an inventively applied catalyst is prepared in the following manner · An alloy bestehenc from approximately 42 wt. ^ Niokel and 58 wt _e $ aluminum is crushed into particles having a diameter of 1.27 cm vein smaller, twice with its own Weight of a 0.5 η sodium hydroxide solution in water treated. When this nickel-aluminum alloy is treated with sodium hydroxide solution, a reaction occurs in which hydrogen evolves and sodium luminate and alumina are formed. The hydrogen is allowed to evolve until the desired conversion of the Aluminum is reached, which is preferably 30 to 85 #. During this reaction, the temperature of the mixture is kept at its boiling point by external heating. After the desired conversion has been achieved, the reaction is quenched with cold water. The catalyst is then repeatedly washed with tap water equal to the weight of the original alloy and at least 15 times. The catalyst is then washed 4 times with methanol and then stored in methanol for use in the process. Optionally, the catalyst can be washed with ethanol, dioxane or other suitable liquids and stored therein. Typical Katalyaatormasaen, as iie are produced in the manner described above, are indicated in the following

_ 7 _ 909886/1239

BATH. ORIQf NAt.

Composition wt. 20th 2 22nd 3 1 42 i3 55 , 0 18th , 5 Yi * 4 22nd , 4 44 f3 .3 ΎΙ ti

Catalyst approach Mr.

aluminum Iickel

Al * Ou. 3 H ₁ O

100.0 100.0 100.0

Ee nurcte also found that the inventive method works satisfactorily with feeds containing relatively high levels of n-olefins and cyeloalefins Process works in the same way using aromatic feeds, never e.g. benzene. In 'previously known methods it is always required to recover the olefin and aromatic content To keep components of the feed as low as possible.

Furthermore, it is well known that nickel catalysts are easy be poisoned by sulfur. It has now been found, however, that when using the catalysts described here, the catalyst » activity even after prolonged use containing sulfur Loadings remain high.

Another novel and unexpected result »as it is according to the invention is achieved is the high speed with which the feed can be converted while the same is passed through the reaction vessel. Me the following table explains typical rough-time yields, heating values and specific ones Densities of the product gases, such as those with various carbon hydrogen charges can be achieved using the novel catalyst *.

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- 8 ! Bd i β before exiting with different loads

Charging properties Propane Hexmn Naphtha Kerosene

O / H ratio 4.47 5.11 5.42 5.85

ASTM boiling point range ⁰ C - 69 75-90 127-229

working conditions

Product gas

Space-time yield

cm ³ catalyst / h 674 605 289 215

Properties of the gas according to
cleaning

higher calorific value Kcal / m ³ 8,798 8,522 7,862 6,356

specific weight

(air = 1.00) 0.579 0.560 0.508 0.467

In the case of maximum demands on a gas system, ie at so-called peak times, it is expedient for a corresponding method to be able to work at high space velocities, since the greatest possible amount of gas is to be produced in the shortest possible time. It has now been found due to the application of the novel catalyst of the invention that with a decrease in catalyst activity it is possible, the initially high space velocity thereby maintain that the temperature of the catalyst bed is increased · If, for example having the catalyst bed an original temperature of 398 ⁰ C, can this temperature can be increased up to about 454 ^° C. in order to compensate for the loss of activity of the catalyst without this essentially affecting the quality of the gas or the rate at which it is produced. The invention will now be explained, for example, with reference to the accompanying drawing, which is a schematic flow diagram of the gasification process. In the drawing, the reference numeral 1 shows a storage vessel in which the charge is stored. This feed represents a hydrocarbon in the manner described above.

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BATH ORIGINAL

The hydrocarbon feed is pumped through a heat exchanger 2, in which it is evaporated and then mixed with water vapor from the boiler 3 in the mixture 4. The mixture is maintained at elevated pressure depending on the type of feed and the desired composition of the product gas. The flow of the intimately mixed hydrocarbon vapors and the water vapor then passes through a heat exchanger 5, where the mixture is preheated to the heating temperature, which runs to 343 »3 to 566 ⁰ C depending on the working conditions, the type of The mixture of hydrocarbon vapors and water vapor then enters the reaction vessel 6 and passes through a catalyst bed. The gasification reactions take place here and the hydrocarbons are completely gasified , Hydrogen, carbon monoxide, carbon dioxide and undecomposed water vapor, exits the reaction vessel and in heat exchange with the introduced feed stream in the preheater 5 « Additional cooling of the exiting stream is achieved in a heat exchanger 7, where the excess heat for the steam generation supply or other process heat can be applied, and Sasser is condensed. The cooled gas flow then passes to a gate direction 8 for the carbon dioxide removal of conventional construction * where the carbon dioxide flow 9 is separated from the product gas flow obtained, as stated above it becomes unnecessary to remove the carbon dioxide from the product gas when such a gas is used for the supply of a peak demand. In such a package, the gas is suitable for consumption after it leaves the heat exchanger 7. . ₁₀ .

909886/1239 BATH ORIGINAL

The equipment described above has worked successfully on a variety of hydrocarbon feeds used to produce a high methane gas. Her invention is as follows further explained with the aid of a number of exemplary embodiments.

example 1

An apparatus according to FIG. 1 is used for the gasification of n-hexane applied. The hydrogen-hexane weight ratio is changed successfully from 1.6: 1 to 2.8: 1 without leaving the catalyst Carbon deposits are formed, and the space-time Yields are up to 6-5 m of catalyst / h, with practically no hexane breaking through the feed. Working conditions are reproduced below:

Catalyst volume: "Pressure of the reactor:

Temperature in the middle of the bed:

Water vapor-hexane weight ratio hexane space velocity

Product gas composition (anhydrous) CO. H ₁ CH ₄

200 3
cm a Ψ 27.4 kg / cm ,8th 450 ⁰ C , 3 1, 62 3 t9 1330 kg / h / m , 0 catalyst Mole 20th 2 76 100

Total: The removal of carbon dioxide down to 2 Μο1 · $ des

Product gas leads to the following properties: Composition #

CO, 2.0

H, 2.8

CH 95.2

Total 100.0

specific weight (air = 1.00) 0.560 _a

higher calorific value 8522 Kcal / in

The conversion of the hexane over the catalyst amounts to sicü $ 100 and no deactivation of the catalyst is observed.

Example 2

It becomes the device according to the Mg · 1 for gasifying a light kerosene with a density of 48.8 ° API and a »boiling» - range from 183 to 230 ° C applied. The kerosene contains the following Components: 9OW6 // 2U9 - Il ä

BATH ORIGINAL

Composition: Vol. #

Aromatics 5.3

olefinic constituents 1.1

saturated ingredients 93.6

100.0

No carbon is deposited on the catalyst and it does the hydrocarbon does not break through · The working conditions are given below. Catalyst lumen 100 cm

Reactor pressure 27.4 kg / cm

Temperature in the middle of the bed Waaserdeepf kerosene weight ratio 2.03 Kerosene space velocity 3620 kg / m cat. Product composition (anhydrous) Mole i>

H ₁ + CfO 1.1

0O ₁ 23.6

H. 18.1

57.2

100.0 Removal of carbon dioxide down to 2 months

Product gas leads to the following properties: Composition MoI ₀ ^

K ₁ + 00 1.4

0O ₁ 2.0

B ^ 23.2

OH ₄ 73.4

100.0

specific weight (air = 1.00) 0.467 _a

higher calorific value 6356 Kcal / m

Example 3

JBs is iie device after the Pig. 1 for gassing a mixed paraffinic hydrogen oxide feed used. The feed is essentially light naphtha

The corresponding characteristics of the feed are as follows:

specific gravity 70.3 ° API

ASTM Deatillationsbereioh 75-9O ⁰ C

Composition% by volume

aromatic constituents 2.0

olefinic ingredients

saturated constituents 98 »0

100.0

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No carbon is deposited on the catalyst and it occurs no breakthrough of the hydrocarbon an “The working conditions are given as follows:

Catalyst volume 25 cm _t

Reactor pressure 25 kg / cm

! temperature in the middle of the bed 502 ⁰ C

Water vapor naphtha weight ratio 2.16 _B

Baphtha room speed 5260 kg / h m

catalyst

Product gas composition (anhydrous) mol. ^

CO 0.2

CO ₁ 21.5

H ₈ . 12.1

CH ₄ 66.2

100.0

Removing the carbon dioxide down to 2 moles “# des

Product gas leads to the following properties:

Composition CO CO ₈

H. • CH ₄

100.0

specific weight (air = 1.00) 0.508

higher heat value 7.862 Kcal / m

Example 4

The apparatus of FIG. 1 is used for gasifying a saturated, aliphatic hydrocarbon feed. This charge represents a commercial charge made up essentially of propane _o The composition of the charge is given below:

Composition MbIo ^

Propane 94.5

Propylene 2.5

Ethane 1.5

Isobutane 1.0

Normal butane 0.5

100.0

Catalyst volume: 25 cm

Reactor pressure 25 kg / cm

! Temperature in the middle of the bed 477 ⁰ C

Water vapor propane weight ratio 1.26 _a

Propane space velocity 13360 kg / h m

catalyst

ο, 3 2, 0 15, 1 3 £ f 6th

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Product gas composition (anhydrous) Mol #

CO 0.1

00 _e 16.8

H ₈ 1.9

OH ₄ gfflfl

O ₁ H ₆ 0.1

O ₃ H ₈ 1.0

100.0

Removal of the carbon dioxide ice down to 2 moles of the product gas results in the following properties:

composition

00 0.1

0O ₈ 2.0

H, 2.2

OH ₄ 94.4

O ₈ H ₆ 0.1

O ₃ H ₈ 1.2

100.0

specific gravity (, air = 1.00) 0.576

higher calorific value 8710 Kcal / m

Example 5

It is the device of FIG. 1 for the gasification of a aromatic hydrocarbon feed, benzene, applied, Carbon is not deposited due to the high water vapor to benzene ratio Typical working conditions are given below:

Catalyst volume 25 cm

Reactor pressure 27 »4 kg / cm

{temperature in the middle of the bed: 485 ^° C

Water vapor-benzene weight ratio _β 4.42

Benzene Eaum speed 5190 kg / h m catalyst

Product gas composition (anhydrous) #

N σο

gg)

+ σο Ι579

00, 30.7

H ₈ 31.3

OH ₄ 36.7

° βΗβ 0.

.4

3.00.0

- 14 -

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The removal of unreacted benzenes and carbon dioxide up down to 2 moles # of product gas results in the following properties :

Composition Mol, 9t

N ₁ + CO 1.3

C0 _a 2.0

H, 44.3

OH ₄ 52.4

100.0

specific gain (air = 1.00) 0.364

higher calorific value 5320 Kcal / m

Example 6

The device shown in Pig »1 is used for gasifying jet fuel (JP -4). The corresponding properties of this charge are given as follows: specific gravity 5 * · 65 ^Ο API

ASTM distillation range: 90 to 248 ⁰ O

Sulfur 0.00429b

Composition VoI, ^

aromatic constituents 10.6

saturates 84.8

olefinic constituents 4.6

100.0

There is no carbon deposition on the catalyst and

the working conditions are given below:

Catalyst volume 25 cm _t

Reactor pressure 24.5 kg / cm

maximum bed temperature 482 ^° C

Water vapor fuel weight ratio 2.36 fuel space velocity 4070 kg / h b? Catalyst

Product gas composition (anhydrous) Mol « j»

00 0.2

00, 22.5

14.5 62.6

0.0

β 1 * ^

100,

The removal of carbon dioxide down to 2 moles of the product » gases leads to the following properties 1

- 15 909886/1239

composition

OO 0.3

CO. 2.0

18.3 79.1 0.3

100.0

Specific weight (.air = 1.00) 0.492 higher calorific value 6780 Kcal / m

Example 7

Eb is the device for gasification shown in FIG. 1 of a technical grade n-octane applied «The typical working conditions are the following:

s catalyst volume 100 cm _%

Reactor pressure 26.2 kg / cm

Temperature in the middle of the bed 380.5 ⁰ C water vapor-octane weight ratio _s 1. 88

Ootane space velocity 8490 kg / h m catalyst

Prod uktgae additive etching (anhydrous) Mol »^ N, + CO 1,2

QO ₁ 21.3

H, 12.1

CH ₄ 65.4

100.0

When the carbon dioxide is removed down to 2 moles of the product gas

it has the following properties:

Composition Mol. »

N ₁ + 00 1.4

CO ₁ 2.0

H ₁ 15.1

CH ₄ 81.5

100.0

specific weight (air »1.00) 0.497 _a

higher calorific value 6785 Kcal / m

The conversion of the octane over the catalyst is 100% and no deactivation of the catalyst is observed On the basis of the above exemplary embodiments, it can be seen that the method leads to the formation of a high methane gas continuously with a variety of hydrocarbons, especially the Containing 2 or more carbon atoms or mixtures thereof when a reaction with steam occurred in the presence of the indicated novel catalyst 909886/1239

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Claims (1)

ion ιαιι η α ι ισ Dipi-ing. Walter Meissner -> ife * Dipi.-ing. Herbert Tischer 1 BERLIN 33, HERBERTSTRASSE 22 1 R Λ ^ Λ Λ 7 MUNICH Telephone: 8 87 72 37 - Wireword: Invention Berlin I O H vJ H H / Poetscheckkonto: W. Meissner, Berlin West 12282 Bank account: W. Meissner, Berliner Bank A.-6., Depka 36, ₁ pppi im qq / rPIINFUl / AI m rtpii '"» Berlln-Halensee, Kurfürstendamm I30 ¹ BERLIN 33 (GRUNEWALD) , the, Herbertstrasse 22 Xnatitute of Qaa Technology Pap t talks Continuous process for producing a methane rich gases · from Kohlenwaaerstoffbesohiokungen, thereby known that the feed is steamed Terdampf te charging then old water vapor ia esjeswart one novel Hiokel-Ioaerde-HuslniuB-Jtatalyeators with increased. Pressure and increased! Temperature τοη 343-566 * 0 with the formation of a Oases sur ÄeäBion is brought, this is essential methane » Carbon dioxide, hydrogen and small amounts of carbon monoxide contains. 2 · A method according to Ansnraoh I ₉ characterized gekennseiohnet that at a pressure τοη 5 to 30 kg / os. is being worked 3 · The method according to claim 2 «characterized in that the Carbon dioxide is removed from the product gas 4 · Proceedings according to one of the Toranachesen speeches, thereby characterized in that the catalyst which can be used 25 to 60 uew.jl nickel, 10 to 60 uew.?t alumina and the rest Contains aluminum. 5 · Method according to one of the claims preceding the goal, characterized characterized in that a proportion of water vapor su charge τοη a maximum of 4.5il is applied to the weight unit. 6. The method according to any one of the goal-related claims, characterized gekennseiohnet that the hydrocarbon feed eia a gaseous hydrocarbon, a liquid hydrocarbon Almost all gaseous and liquid hydrocarbons are involved. 909886/1239 ' ² ' applied to the working conditions of the reaction vessels gaseous aind. 7 »Vex 'drive ηaoh. one of the preceding claims marked * that as Xohlaahawasaerstoff "charge one to Propane rich feed is applied » 8. The method according to claims 1 feie 6 _V characterized in that ale Beachiolciuig n-Höxan »DUeennotoren-Brenaetof ^ * light kerosene, benzene, light Haßhtha, n-ootan or an Austrian ciers sameH is used. 9. The method according to any one of the preceding claims _r, characterized in that a Wasssräampf-Kohlenwaeaeratoff weight ratio of at least l, 26il is applied. ρί-ί-- h tm 909886/1239
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